Silicon nitride and silicon oxide deposition methods using fluorine inhibitor

ABSTRACT

Methods of depositing material on a surface of a substrate are disclosed. The methods include using a fluorine reactant to reduce a growth rate per cycle of silicon oxide and/or silicon nitride deposited onto a surface of a substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of and priority to U.S. ProvisionalApplication No. 63/047,187, filed on Jul. 1, 2020 in the United StatesPatent and Trademark Office, the disclosure of which is incorporatedherein in its entirety by reference.

FIELD OF INVENTION

The present disclosure generally relates to methods of depositingmaterial onto a surface of a substrate, to structures formed using themethod, and to systems for depositing the material.

BACKGROUND OF THE DISCLOSURE

During the formation of electronic devices, such as semiconductordevices, it may be desirable to fill a gap (e.g., a trench, via, orspace between features) on a surface of a substrate with insulatingmaterial, such as silicon nitride or silicon oxide. Atomic layerdeposition (ALD) can be used to conformally deposit silicon nitride orsilicon oxide over gaps and thereby fill the gaps.

In some cases, a plasma-enhanced process, such as plasma-enhanced ALD(PEALD), can be used to deposit silicon nitride or silicon oxide.Plasma-enhanced processes can be operated at relatively low temperaturesand/or exhibit relatively high deposition rates, compared to methodsthat do not employ a plasma.

Unfortunately, silicon nitride and silicon oxide deposited using PEALDon high aspect-ratio features (e.g., gaps having an aspect ratio ofthree or more) tend to form voids in the deposited material, becauseless material is deposited at the bottom of a feature (e.g., on a bottomsurface or on a side surface near the bottom of the gap—compared to aside surface of the gap at or near the top of the gap). The poorconformality and/or undesired deposition profile of the depositedmaterial can be attributed to a loss of activated species, such asradicals, that can occur by surface recombination of the radicals at,for example, the sidewalls of the gaps.

Efforts to improve low conformality and/or gap-fill ability of PEALDdeposited material have focused on tuning process parameters, such as RFpower, plasma exposure time, pressure, and the like, so as to provideadequate activated species, such as radicals, near the bottom of afeature, so as to increase an amount of material deposited at the bottomof the feature. However, because recombination of radicals is anintrinsic phenomenon, such efforts have been limited. Moreover, recentdevice manufacturing specifications often demand low plasma near thebottom of a feature. For such applications, conventional methods thatinclude increasing activated species and/or activated species energy atthe bottom of a feature cannot be used.

To overcome such problems, several techniques have been proposed. Forexample, U.S. Pat. No. 9,887,082 to Pore et al. discloses a method forfilling a gap. The method includes providing a precursor into a reactionchamber to form adsorbed species on a surface of a substrate, exposingthe adsorbed species to a nitrogen plasma to form species at the top ofthe feature that include nitrogen, and providing a reactant plasma tothe reaction chamber, wherein nitrogen acts as an inhibitor to thereactant, resulting in less material being deposited at the top of thegap, compared to traditional PEALD techniques. Such techniques canresult in silicon nitride with fewer voids or seams than traditionaltechniques, but voids and seams within the silicon nitride can stillform, particularly in higher aspect ratio gaps. Further, a wet etch rateof silicon nitride deposited using such techniques can be undesirablyhigh for some applications.

Accordingly, improved methods for depositing material suitable forfilling gaps on a surface of a substrate and structures formed usingsuch methods are desired. Any discussion of problems and solutionsinvolved in the related art has been included in this disclosure solelyfor the purposes of providing a context for the present invention andshould not be taken as an admission that any or all of the discussionwere known at the time the invention was made.

SUMMARY OF THE DISCLOSURE

Various embodiments of the present disclosure relate to methods ofdepositing material onto a surface of a substrate—e.g., depositingmaterial over features on the substrate surface—that are suitable forfilling gaps on the surface of the substrate. While the ways in whichvarious embodiments of the present disclosure address drawbacks of priormethods and systems are discussed in more detail below, in general,various embodiments of the disclosure provide improved methods suitablefor filling the gaps on the surface while mitigating void or seamformation that might otherwise occur using traditional techniques.

In accordance with embodiments of the disclosure, a method of depositingone or more of silicon nitride and silicon oxide onto a surface of asubstrate is provided. The method can include providing a fluorinereactant to the reaction chamber for a fluorine reactant pulse,providing a silicon precursor to the reaction chamber for a siliconprecursor pulse, providing one or more of a nitrogen reactant and anoxygen reactant to the reaction chamber for a reactant pulse, andoptionally providing a hydrogen reactant to the reaction chamber for ahydrogen reactant pulse. When hydrogen is provided, the hydrogen can beintroduced to a reaction chamber separately or can be mixed with anotherreactant, for example, the nitrogen reactant, and introduced to thereaction chamber at the same time with the nitrogen reactant. Inaccordance with examples of these embodiments, silicon precursor caninclude one or more of a silane, a halogensilane, and an organosilane.The nitrogen reactant can include one or more of nitrogen (N₂), N₂O, andNO and/or the oxygen reactant can include, for example, O₂. The fluorinereactant can include one or more of NF₃, CF₄, C₂F₆, SF₆, NH₂F, C₃F₈, andF₂. The hydrogen reactant can include or more of hydrogen (H₂), NH₃,N₂H₄, and N₂H₂. As set forth in more detail below, various combinationsof the reactants can be continuously supplied to the reaction chamberduring two or more method steps. Additionally or alternatively, in somecases, two or more of the method steps can overlap in time and space. Insome cases, an order of two or more steps may be specified. In somecases, it may be specified that two or more steps do not overlap. Inthis context, overlap can mean that the reactants enter or are withinthe same reaction chamber at the same time (e.g., without an interveningpurge). In accordance with further examples of the disclosure, one ormore of the reactants may be exposed to a plasma to form activatedspecies. The plasma can be a direct or remote plasma. Methods describedherein can be used to form silicon oxide and/or silicon nitride suitablefor filling a gap on a surface, suitable for forming a hard mask, or thelike.

In accordance with yet further exemplary embodiments of the disclosure,a deposition apparatus configured to perform a method as describedherein is provided.

In accordance with yet further exemplary embodiments of the disclosure,a structure comprises silicon oxide and/or silicon nitride depositedaccording to a method described herein.

These and other embodiments will become readily apparent to thoseskilled in the art from the following detailed description of certainembodiments having reference to the attached figures; the invention notbeing limited to any particular embodiment(s) disclosed.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

A more complete understanding of exemplary embodiments of the presentdisclosure can be derived by referring to the detailed description andclaims when considered in connection with the following illustrativefigures.

FIG. 1 illustrates a method in accordance with at least one embodimentof the disclosure.

FIGS. 2-5 illustrate timing sequences of methods in accordance withembodiments of the disclosure.

FIG. 6 illustrates a method in accordance with at least one embodimentof the disclosure.

FIGS. 7 and 8 illustrate timing sequences of methods in accordance withembodiments of the disclosure.

FIG. 9 illustrates a structure including a gap and a layer partiallyfilling the gap, wherein the layer is relatively thin near the bottom ofthe gap.

FIG. 10 illustrates a structure including a gap and a layer partiallyfilling the gap, wherein the layer is relatively thick near the bottomof the gap according to an embodiment of the present disclosure.

FIG. 11 illustrates structures during a gap filling method according toat least one embodiment of the present disclosure.

FIG. 12 illustrates a system in accordance with at least one embodimentof the disclosure.

It will be appreciated that elements in the figures are illustrated forsimplicity and clarity and have not necessarily been drawn to scale. Forexample, the dimensions of some of the elements in the figures may beexaggerated relative to other elements to help improve understanding ofillustrated embodiments of the present disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it willbe understood by those in the art that the invention extends beyond thespecifically disclosed embodiments and/or uses of the invention andobvious modifications and equivalents thereof. Thus, it is intended thatthe scope of the invention disclosed should not be limited by theparticular disclosed embodiments described below.

The present disclosure generally relates to methods of depositingmaterial onto a surface of a substrate, to deposition apparatus forperforming the methods, and to structures formed using the methods. Themethods and systems as described herein can be used to processsubstrates to form, for example, electronic devices. By way of examples,the systems and methods described herein can be used to deposit siliconnitride and/or silicon oxide onto a surface of a substrate, which caninclude high-aspect ratio features to, for example, fill gaps within orbetween the high-aspect ratio features.

In this disclosure, “gas” may include material that is a gas at normaltemperature and pressure, a vaporized solid and/or a vaporized liquid,and may be constituted by a single gas or a mixture of gases, dependingon the context. A gas other than the process gas, i.e., a gas introducedwithout passing through a gas distribution assembly, such as ashowerhead, other gas distribution device, or the like, may be used for,e.g., sealing the reaction space, which includes a seal gas such as arare gas. In some embodiments, the term “precursor” refers generally toa compound that participates in the chemical reaction that producesanother compound, and particularly to a compound that constitutes a filmmatrix or a main skeleton of a film, whereas the term “reactant” refersto a compound, other than precursors, that activates a precursor,modifies a precursor, or catalyzes a reaction of a precursor, whereinthe reactant may provide an element (such as O, N, C) to a film matrixand become a part of the film matrix, when RF power is applied. The term“inert gas” refers to a gas that does not take part in a chemicalreaction and/or a gas that excites a precursor when RF power is applied,but, unlike a reactant, may not become a part of a film matrix to anappreciable extent.

As used herein, the term “substrate” may refer to any underlyingmaterial or materials that may be used to form, or upon which, a device,a circuit, or a film may be formed. A substrate can include a bulkmaterial, such as silicon (e.g., single-crystal silicon), other Group IVmaterials, such as germanium, or compound semiconductor materials, suchas Group III-V or Group II-VI semiconductors, and can include one ormore layers overlying or underlying the bulk material. Further, thesubstrate can include various topologies, such as recesses, lines, andthe like formed within or on at least a portion of a layer of thesubstrate.

In some embodiments, “film” refers to a layer continuously extending ina direction perpendicular to a thickness direction substantially withoutpinholes to cover an entire target or concerned surface, or simply alayer covering a target or concerned surface. In some embodiments,“layer” refers to a structure having a certain thickness formed on asurface or a synonym of film or a non-film structure. A film or layermay be constituted by a discrete single film or layer having certaincharacteristics or multiple films or layers, and a boundary betweenadjacent films or layers may or may not be clear and may or may not beestablished based on physical, chemical, and/or any othercharacteristics, formation processes or sequence, and/or functions orpurposes of the adjacent films or layers.

The term “cyclic deposition process” or “cyclical deposition process”can refer to the sequential introduction of precursors (and/orreactants) into a reaction chamber to deposit a layer over a substrateand includes processing techniques such as atomic layer deposition(ALD), cyclical chemical vapor deposition (cyclical CVD), and hybridcyclical deposition processes that include an ALD component and acyclical CVD component.

As used herein, the term “atomic layer deposition” (ALD) may refer to avapor deposition process in which deposition cycles, preferably aplurality of consecutive deposition cycles, are conducted in a processchamber. Typically, during each cycle, a precursor is introduced and maybe chemisorbed to a deposition surface (e.g., a substrate surface or apreviously deposited underlying surface such as material from a previousALD cycle), forming a monolayer or sub-monolayer that does not readilyreact with additional precursor (i.e., a self-limiting reaction).Thereafter, a reactant (e.g., another precursor or reaction gas) maysubsequently be introduced into the process chamber for use inconverting the chemisorbed precursor to the desired material on thedeposition surface. Typically, this reactant is capable of furtherreaction with the precursor. Further, purging steps may also be utilizedduring each cycle to remove excess precursor from the process chamberand/or remove excess reactant and/or reaction byproducts from theprocess chamber after conversion of the chemisorbed precursor. Further,the term “atomic layer deposition,” as used herein, is also meant toinclude processes designated by related terms, such as chemical vaporatomic layer deposition, atomic layer epitaxy (ALE), molecular beamepitaxy (MBE), gas source MBE, or organometallic MBE, and chemical beamepitaxy when performed with alternating pulses of precursorcomposition(s), reactive gas, and purge (e.g., inert carrier) gas. PEALDrefers to an ALD process, in which a plasma is applied during one ormore of the ALD steps.

As used herein, silicon nitride refers to a material that includessilicon and nitrogen. Silicon nitride can be represented by the formulaSi_(x)N_(y) (e.g., Si₃N₄). In some cases, the silicon nitride may notinclude stoichiometric silicon nitride. In some cases, the siliconnitride can include other elements, such as carbon, oxygen, hydrogen, orthe like.

As used herein, silicon oxide refers to a material that includes siliconand oxygen. Silicon oxide can be represented by the formula SiO_(x)(e.g., SiO₂). In some cases, the silicon oxide may not includestoichiometric silicon oxide. In some cases, the silicon oxide caninclude other elements, such as carbon, nitrogen, hydrogen, or the like.

As used herein, silicon oxynitride refers to a material that includessilicon, oxygen, and nitrogen. Silicon oxynitride can be represented bythe formula SiO_(x)N_(y). In some cases, the silicon oxynitride caninclude other elements, such as carbon, hydrogen, or the like. Siliconoxynitride can include silicon oxide and silicon nitride.

Further, in this disclosure, any two numbers of a variable canconstitute a workable range of the variable as the workable range can bedetermined based on routine work, and any ranges indicated may includeor exclude the endpoints. Additionally, any values of variablesindicated (regardless of whether they are indicated with “about” or not)may refer to precise values or approximate values and includeequivalents, and may refer to average, median, representative, majority,etc. in some embodiments. Further, in this disclosure, the terms“including,” “constituted by” and “having” can refer independently to“typically or broadly comprising,” “comprising,” “consisting essentiallyof,” or “consisting of” in some embodiments. In this disclosure, anydefined meanings do not necessarily exclude ordinary and customarymeanings in some embodiments.

In this disclosure, “continuously” can refer to one or more of withoutbreaking a vacuum, without interruption as a timeline, without anymaterial intervening step, without changing treatment conditions,immediately thereafter, as a next step, or without an interveningdiscrete physical or chemical structure between two structures otherthan the two structures in some embodiments.

Turning now to the figures, FIG. 1 illustrates a method 100, suitablefor depositing one or more of silicon nitride and silicon oxide onto asurface of a substrate within a reaction chamber in accordance with atleast one embodiment of the disclosure. Method 100 includes the steps ofproviding a substrate within a reaction chamber (step 102), providing afluorine reactant to the reaction chamber for a fluorine reactant pulse(step 104), providing a silicon precursor to the reaction chamber for asilicon precursor pulse (step 106), and providing one or more of anitrogen reactant and an oxygen reactant to the reaction chamber for areactant pulse (step 108). As illustrated, method 100 can also includeproviding a hydrogen reactant to the reaction chamber for a hydrogenreactant pulse (step 110). Method 100 can include an a cyclical (e.g.,ALD) process, such as a PEALD process.

Step 102 includes providing at least one substrate into a reactionchamber and bringing the substrate to a desired temperature. Thereaction chamber may include a PEALD reaction chamber. A temperaturewithin the reaction chamber during step 102 can be brought to atemperature for subsequent processing—e.g., between about −10° C. andabout 1000° C. or about 75° C. to about 600° C. Similarly, a pressurewithin the reaction chamber may be controlled to provide a reducedatmosphere in the reaction chamber for subsequent processing. Forexample, the pressure within the reaction chamber can be brought to lessthan 5000 Pa, or less than 2000 Pa, or less than 1000 Pa, or be betweenabout 0.0001 Pa and about 101325 Pa or about 10 Pa and about 13333 Pa.

During step 104, a surface of a substrate is exposed to a fluorinereactant. During this step, the temperature and/or pressure can be asset forth above in connection with step 102. In accordance with examplesof the disclosure, a plasma is applied during at least a portion of step104 of providing a fluorine reactant to the reaction chamber. The plasmacan be a remote plasma, such that activated fluorine species areintroduced to the reaction chamber, or a direct plasma, where activatedfluorine species are formed within the reaction chamber. In accordancewith examples of the disclosure, the activated fluorine species canpreferentially react with a top surface of a feature, such as a gap,such that the effects of the fluorine that reacts with the substratesurface is greater near a top of the feature, relative to a bottom ofthe feature. The presence of fluorine on a surface increases anincubation and/or reduces a growth rate per cycle of subsequentlydeposited silicon nitride and/or silicon oxide.

A power to produce activated fluorine species during step 104 can begreater than OW and about 10000 W or about 50 W and about 3000 W. Afrequency of the power can be between about 430 kHz and about or about13.56 MHz.

In accordance with examples of the disclosure, a temperature within thereaction chamber can be relatively low—e.g., less than 25° C. or lessthan 550° C. to prevent or mitigate etching of material during step 104.

The fluorine reactant provided during step 104 can include any suitablefluorine-containing reactant. By way of examples, the fluorine reactantcan be or include one or more of NF₃, CF₄, C₂F₆, SF₆, NH₂F, C₃F₈, andF₂. In some cases, the fluorine reactant can be provided to the reactionchamber and/or a remote plasma unit mixed with a carrier gas, such as aninert gas. Suitable inert or carrier gases include, for example, N₂, Ar,He, Ne, Xe.

Exemplary fluorine reactant flow rates during step 104 can be about 1sccm to about 1000 sccm or about 2 sccm to about 100 sccm. A pulse timefor fluorine reactant flow during step 104 can be 0.01 seconds to about600 seconds or about 1 second to about 300 seconds.

In accordance with examples of the disclosure, process conditions forstep 104 can be controlled to mitigate etching of underlying materialand/or to control areas that are affected by fluorine reactant. Forexample, process conditions can be selected, such that growth rates ofsubsequently formed material are lower in top areas (e.g., the top 25%or top 10%) of features, compared to the remainder of the features.Further, when a hydrogen reactant is used, the hydrogen reactant canpromote growth in the lower/remainder portions of the features.

During step 106, a silicon precursor is provided to the reaction chamberfor a silicon precursor pulse. A pressure and temperature within thereaction chamber can be as noted above in connection with step 102. Insome cases, a substrate, gas distribution system (e.g., showerhead),and/or reaction chamber wall temperature during step 106 can be higherthan the substrate, gas distribution system, and/or reaction chamberwall temperature during step 104—e.g., to facilitate deposition duringstep 106 and steps 108 and 110. In accordance with examples of thedisclosure, a plasma is not provided during step 106.

The silicon precursor provided during step 106 can include one or moreof a silane, a halogensilane, and an organosilane. Exemplaryhalogensilanes include one or more of dichlorosilane, diiodosilane,hexachlorodisilane, octachlorotrisilane, dibromosilane, tribromosilane,trichlorosilane (HSiCl₃), chlorosilane (H₃SiCl), silicon tetrachloride(SiCl₄), bromosilane (H₃SiBr), triiodosilane (HSiI₃), iodosilane(H₃SiI), diiiodosilane (H₂Si₂I₄), H₄Si₂I₂, and H₅Si₂I. Exemplaryorganosilanes include one or more of an aminosilane and a heterosilane.By way of particular examples, the silicon precursor can include one ormore of tris(dimethylamino)silane, bis(tert-butylamino)silane,di(sec-butylamino)silane, trisilylamine, neopentasilane,bis(dimethylamino)silane, (dimethylamino)silane(DMAS),bis(diethylamino)silane (BDEAS), bis(ethylmethylamino)silane (BEMAS),tetrakis(dimethylamino)silane (TKDMAS), trimethylsilane (SiH(CH₃)₃),tetramethylsilane (Si(CH₃)₄), silane, tetra(ethoxy)silane (TEOS,Si(OC₂H₅)₄), tris(tert-butoxy)silanol (TBOS), tris(tert-pentoxy)silanol(TPSOL), and dimethyldichlorosilane (Si(OC₂H₅)₄, Si(CH₃)₂(OCH₃)₂).

Exemplary silicon precursor flow rates during step 106 can be about 1sccm to about 500 sccm or about 3 sccm to about 100 sccm. A pulse timefor silicon precursor flow during step 106 can be 0.1 seconds to about10 seconds or about 0.2 second to about 3 seconds.

During step 108, one or more of a nitrogen reactant and an oxygenreactant are provided to the reaction chamber for a reactant pulse. Atemperature and pressure within the reaction chamber during step 108 canbe the same or similar to the temperature and pressure within thereaction chamber during step 104 or 106.

In accordance with examples of the disclosure, a plasma is appliedduring at least a portion of step 108 of providing one or more of anitrogen reactant and an oxygen reactant to the reaction chamber. Theplasma can be a remote plasma or a direct plasma. A power to produce aplasma during step 108 can be greater than OW and about 10000 W or about50 W and about 3000 W. A frequency of the power can be between about 400kHz and about 60 MHz or about 13.56 MHz.

The nitrogen reactant can include a nitrogen-containing compound, suchas one or more of nitrogen (N₂), N₂O, and NO. Additionally oralternatively, the oxygen reactant can include an oxygen-containingcompound, such as O₂.

Exemplary nitrogen reactant flow rates during step 108 can be about 100sccm to about 50000 sccm or about 5000 sccm to about 30000 sccm. A pulsetime for nitrogen reactant flow during step 108 can be 0.05 seconds toabout 20 seconds or about 0.1 second to about 10 seconds. Exemplaryoxygen reactant flow rates during step 108 can be about 100 sccm toabout 50000 sccm or about 5000 sccm to about 30000 sccm. A pulse timefor oxygen reactant flow during step 108 can be 0.05 seconds to about 20seconds or about 0.05 second to about 10 seconds.

During optional step 110, a hydrogen reactant is provided to thereaction chamber for a hydrogen reactant pulse. A temperature andpressure within the reaction chamber during step 110 can be the same orsimilar to the temperature and pressure within the reaction chamberduring any of steps 104-108, and particularly any of steps 106, 108.

In accordance with examples of the disclosure, a plasma is appliedduring at least a portion of step 110. The plasma can be a remote plasmaor a direct plasma. A power to produce a plasma during step 110 can begreater than OW and about 10000 W or about 50 W and about 3000 W. Afrequency of the power can be between about 400 kHz and about 60 MHz orabout 13.56 MHz.

The hydrogen reactant can include, for example, one or more of hydrogen(H₂), NH₃, N₂H₄, and N₂H₂. Exemplary hydrogen reactant flow rates duringstep 108 can be about 1 sccm to about 5000 sccm or about 10 sccm toabout 500 sccm. A pulse time for hydrogen reactant flow during step 108can be 0.1 seconds to about 15 seconds or about 0.5 second to about 5seconds.

As noted above, use of activated hydrogen and fluorine species canpromote deposition in a lower portion of a feature, compared to a topportion of the feature. This may be particularly the case forhalogensilanes and/or aminosilane silicon precursors.

Steps 106-110 can be considered a deposition cycle, which can berepeated (loop 112) one or more times. Method 100 can further include aloop 114 of repeating steps 104-110.

For example, loop 114 can be repeated a number of times until a gap on asurface of a substrate is filled with the one or more of silicon nitrideand silicon oxide and/or a desired film thickness is reached. Further,although not separately illustrated, any of steps 104-110 can berepeated prior to proceeding to the next step.

Two or more of steps 106-110 can be performed at the same time or mayoverlap—at least partially—in time. For example, steps 106 and 110 mayoverlap or be performed at the same time. Additionally or alternatively,steps 108 and 110 can overlap. Further, as illustrated in more detailbelow, one or more steps—e.g., the steps of providing one or more of anitrogen reactant and an oxygen reactant to the reaction chamber can beperformed continuously during the steps of providing a siliconprecursor, optionally providing a hydrogen reactant, and/or providing afluorine reactant.

Further, unless otherwise noted, steps of method 100 can be performed inany order. In the illustrated example, step 104 occurs before step 106.However, as illustrated below, methods can include a step of introducinga fluorine reactant after one or more deposition cycles. In accordancewith some examples, the step of providing a hydrogen reactant (110) andthe step of providing a fluorine reactant (104) do not overlap withinthe reaction chamber.

FIG. 2 illustrates a timing sequence 200 of a method, such as method100, for forming silicon nitride on the surface of the substrate. Timingsequence 200 includes a fluorine treatment cycle 202 and a depositioncycle 204.

Fluorine treatment cycle 202 can include providing a purge gas,providing a nitrogen reactant, and providing a fluorine reactant for afirst period 206 (e.g., without a plasma) and a second period 208 (witha plasma). The conditions for fluorine treatment cycle 202 can be asdescribed above in connection with steps 104 and 108.

Deposition cycle 204 can include providing a silicon precursor and thenitrogen reactant for a period 210. Then, the reaction chamber can bepurged—e.g., using a purge gas and the nitrogen reactant during period212. While the nitrogen reactant continues to flow, a power to produce aplasma can be applied for a period 214. Then, the reaction chamber canbe purged for a period 216. The gas flowrates can be as described abovein connection with FIG. 1.

Timing sequence 200 can include repeating deposition cycle 204 a numberof times. Further, timing sequence 200 can include repeating fluorinetreatment cycle 202 and deposition cycle 204 a number of times, asdescribed above in connection with FIG. 1. In the illustrated example, aseparate hydrogen reactant is not provided during method 200.

FIG. 3 illustrates a timing sequence 300 of a method, such as method100, for forming silicon nitride on the surface of the substrate with ahydrogen reactant. Timing sequence 300 includes a fluorine treatmentcycle 302 and a deposition cycle 304.

Fluorine treatment cycle 302 can include providing a purge gas,providing a nitrogen reactant, and providing a fluorine reactant for afirst period 306 (e.g., without a plasma) and a second period 308 (witha plasma), as described above in connection with fluorine treatment step202.

Deposition cycle 304 can include providing a silicon precursor and thenitrogen reactant for a period 310. Then, the reaction chamber can bepurged—e.g., using a purge gas, the nitrogen reactant, and the hydrogenreactant during period 312. While the nitrogen reactant and hydrogenreactant continue to flow, a power to produce a plasma can be appliedfor a period 314 to produce nitrogen and hydrogen activated species.Then, the reaction chamber can be purged for a period 316.

Timing sequence 300 can include repeating deposition cycle 304 a numberof times. Further, timing sequence 300 can include repeating fluorinetreatment cycle 302 and deposition cycle 304 a number of times, asdescribed above in connection with FIG. 1. Various gas flowrates duringperiods 306-316 can be as described above in connection with FIG. 1.

FIG. 4 illustrates a timing sequence 400 of a method, such as method100, for forming silicon oxide on the surface of the substrate withoutan additional hydrogen reactant. Timing sequence 400 is similar totiming sequence 200 (except timing sequence 400 includes an oxygenreactant, rather than a nitrogen reactant). Timing sequence 400 includesa fluorine treatment cycle 402 and a deposition cycle 404.

Fluorine treatment cycle 402 can include providing a purge gas,providing a nitrogen reactant, and providing a fluorine reactant for afirst period 406 (e.g., without a plasma) and a second period 408 (witha plasma), as described above in connection with fluorine treatment step202.

Deposition cycle 404 can include providing a silicon precursor and theoxygen reactant for a period 410. Then, the reaction chamber can bepurged—e.g., using a purge gas and the oxygen reactant during period412. While the oxygen reactant continues to flow, a power to produce aplasma can be applied for a period 414 to produce oxygen activatedspecies. Then, the reaction chamber can be purged for a period 416.

Timing sequence 400 can include repeating deposition cycle 404 a numberof times. Further, timing sequence 400 can include repeating fluorinetreatment cycle 402 and deposition cycle 404 a number of times, asdescribed above in connection with FIG. 1.

FIG. 5 illustrates a timing sequence 500 of a method, such as method100, for forming silicon oxide on the surface of the substrate with ahydrogen reactant. Timing sequence 500 includes a fluorine treatmentcycle 502 and a deposition cycle 504.

Fluorine treatment cycle 502 can include providing a purge gas,providing an oxygen reactant (e.g., with a carrier gas), and providing afluorine reactant for a first period 506 (e.g., without a plasma) and asecond period 508 (with a plasma), as described above in connection withfluorine treatment step 202.

Deposition cycle 504 can include providing a silicon precursor and theoxygen reactant for a period 510. Then, the reaction chamber can bepurged—e.g., using a purge gas, the oxygen reactant and/or carrier gas,and the hydrogen reactant during period 512. While the oxygen reactantand hydrogen reactant continue to flow, a power to produce a plasma canbe applied for a period 514 to produce oxygen and hydrogen activatedspecies. Then, the reaction chamber can be purged for a period 516.

Timing sequence 500 can include repeating deposition cycle 504 a numberof times. Further, timing sequence 500 can include repeating fluorinetreatment cycle 502 and deposition cycle 504 a number of times, asdescribed above in connection with FIG. 1.

FIG. 6 illustrates a method 600, suitable for depositing one or more ofsilicon nitride and silicon oxide onto a surface of a substrate within areaction chamber in accordance with at least one embodiment of thedisclosure. Method 600 includes the steps of providing a substratewithin a reaction chamber (step 602), providing a silicon precursor tothe reaction chamber for a silicon precursor pulse (step 604), providingone or more of a nitrogen reactant and an oxygen reactant to thereaction chamber for a reactant pulse (step 606), and providing afluorine reactant to the reaction chamber for a fluorine reactant pulse(step 610). As illustrated, method 600 can also include providing ahydrogen reactant to the reaction chamber for a hydrogen reactant pulse(step 608). Steps 604-610 can be the same or similar to the respectivesteps in method 100; however, in method 600, step 610 is performed aftera deposition cycle including steps 604-608, rather than before thedeposition cycle.

Similar to method 100, method 600 can include repeating steps 604-608(loop 612) and/or repeating steps 604-610 (loop 614).

FIG. 7 illustrates a timing sequence 700 of a method, such as method600, for forming one or more of silicon nitride and silicon oxide onto asurface of a substrate. Timing sequence 700 includes a deposition cycle702 and a fluorine treatment cycle 704.

Deposition cycle 702 can include providing a silicon precursor and areactant and a hydrogen reactant for a period 706. Then, the reactionchamber can be purged—e.g., using a purge gas, the reactant, and thehydrogen reactant during period 708. While the reactant and hydrogenreactant continue to flow, a power to produce a plasma can be appliedfor a period 710 to produce reactant and hydrogen activated reactantspecies. Optionally, the reaction chamber can then be purged for areactant purge period (not illustrated).

Fluorine treatment cycle 704 can include providing a purge gas andreactant (e.g., exclusive of the hydrogen reactant) and a fluorinereactant for a first period 712 (e.g., without a plasma) and a secondperiod 714 (with a plasma), as described above in connection withfluorine treatment step 202. The reaction chamber can then be purged fora fluorine reactant purge period 716.

Timing sequence 700 can include repeating deposition cycle 702 a numberof times. Further, timing sequence 700 can include repeating depositioncycle 702 and fluorine treatment cycle 704 a number of times, asdescribed above in connection with FIG. 6.

FIG. 8 illustrates another timing sequence 800 of a method, such asmethod 600, for forming one or more of silicon nitride and silicon oxideonto a surface of a substrate. Timing sequence 800 includes a depositioncycle 802, a hydrogen cycle 804, and a fluorine treatment cycle 806.

In the illustrated example, deposition cycle 802 includes providing asilicon precursor and a reactant for a period 808. Then, the reactionchamber can be purged—e.g., using a purge gas and the reactant duringperiod 810. While the reactant continues to flow, a power to produce aplasma can be applied for a period 812 to produce reactant activatedspecies. The reaction chamber can then be purged for a reactant purgeperiod 814.

Hydrogen cycle 804 includes providing hydrogen reactant to the reactionchamber and providing power to a plasma unit for a period 816. Thereactor conditions for step 804 can be as described above in connectionwith step 608.

Fluorine treatment cycle 806 can include providing a purge gas andreactant (e.g., exclusive of the hydrogen reactant) and a fluorinereactant for a period 818, during at least a portion of which a plasmais applied. The plasma conditions can be as described above inconnection with FIGS. 1 and 6. The reaction chamber can then be purgedfor a fluorine reactant purge period (not separately illustrated).

Timing sequence 800 can include repeating deposition cycle 802 a numberof times—e.g., prior to proceeding to steps 804 and 806. Further, timingsequence 800 can include repeating deposition cycle 802, hydrogen cycle816, and/or fluorine treatment cycle 818 a number of times, asillustrated in FIG. 8.

FIG. 9 illustrates a structure 900 including gaps 902 and 904 formed ona surface of a substrate 906. Structure 900 includes a silicon nitrideor silicon oxide layer 908 formed according to traditional methodsoverlying substrate 906. As illustrated, silicon nitride or siliconoxide layer 908 has a thickness t1 near a top of gap 902 that is greaterthan a thickness of layer 908 at the bottom of gap 902. As gap 902 fillsusing the traditional technique, a void can form within gap 902.

FIG. 10 illustrates a structure 1000 including gaps 1002 and 1004 formedon a surface of a substrate 1006. Structure 1000 includes one or more ofsilicon nitride and silicon oxide 1008 formed according to a method asdescribed herein—e.g., method 100 or method 600. As illustrated, one ormore of silicon nitride and silicon oxide 1008 has a thickness t1 near atop of gap 1002 that is less than a thickness of layer 1008 at thebottom of gap 1002. As further illustrated in FIG. 11, as gap 1002 fillsusing exemplary methods disclosed herein, no void forms within gap 1002.The conformality of deposited silicon nitride and/or silicon oxide canbe greater than 100% or even greater than 200%, where conformality(%)=side(btm) thickness/side(top) thickness*100.

Turning now to FIG. 12, a reactor system 1200 is illustrated inaccordance with exemplary embodiments of the disclosure. Reactor system1200 can be used to perform one or more steps or sub steps as describedherein and/or to form one or more structures or portions thereof asdescribed herein.

Reactor system 1200 includes a pair of electrically conductiveflat-plate electrodes 4, 2 in parallel and facing each other in theinterior 11 (reaction zone) of a reaction chamber 3. A plasma can beexcited within reaction chamber 3 by applying, for example, HRF power(e.g., 100 kHz, 13.56 MHz, 27 MHz, 2.45 GHz, or any values therebetween)from power source 25 to one electrode (e.g., electrode 4) andelectrically grounding the other electrode (e.g., electrode 2). Atemperature regulator is provided in a lower stage 2 (the lowerelectrode), and a temperature of a substrate 1 placed thereon can bekept at a desired temperature, such as the substrate temperatures notedabove. Electrode 4 can serve as a gas distribution device, such as ashower plate or showerhead. Precursor gas, oxygen and/or nitrogenreactant gases, hydrogen reactant gas, fluorine reactant gas, anddilution/carrier gas, if any, or the like can be introduced intoreaction chamber 3 using one or more of a gas line 23, a gas line 24, agas line 25, and a gas line 27, from sources 21, 22, 20, and 26,respectively, and through the shower plate 4. Although illustrated withfour gas lines 23, 24, 25, and 26, reactor system 1200 can include anysuitable number of gas lines. By way of examples, source 21 cancorrespond to a silicon precursor source, source 22 can correspond toone or more of an oxygen reactant source and a nitrogen reactant source,source 20 can correspond to a hydrogen reactant source, and source 26can correspond to a fluorine reactant source.

In reaction chamber 3, a circular duct 13 with an exhaust line 7 isprovided, through which gas in the interior 11 of the reaction chamber 3can be exhausted. Additionally, a transfer chamber 5, disposed below thereaction chamber 3, is provided with a seal gas line 24 to introduceseal gas into the interior 11 of the reaction chamber 3 via the interior16 (transfer zone) of the transfer chamber 5, wherein a separation plate14 for separating the reaction zone and the transfer zone is provided (agate valve through which a substrate is transferred into or from thetransfer chamber 5 is omitted from this figure). The transfer chamber isalso provided with an exhaust line 6. In some embodiments, thedeposition and/or fluorine treatment steps are performed in the samereaction space, so that two or more (e.g., all) of the steps cancontinuously be conducted without exposing the substrate to air or otheroxygen-containing atmosphere.

In some embodiments, continuous flow of a carrier gas to reactionchamber 3 can be accomplished using a flow-pass system (FPS), wherein acarrier gas line is provided with a detour line having a precursorreservoir (bottle), and the main line and the detour line are switched,wherein when only a carrier gas is intended to be fed to a reactionchamber, the detour line is closed, whereas when both the carrier gasand a precursor gas are intended to be fed to the reaction chamber, themain line is closed and the carrier gas flows through the detour lineand flows out from the bottle together with the precursor gas. In thisway, the carrier gas can continuously flow into the reaction chamber,and can carry the precursor gas in pulses by switching between the mainline and the detour line, without substantially fluctuating pressure ofthe reaction chamber.

Reactor system 1200 can include one or more controller(s) 26 programmedor otherwise configured to cause one or more method steps as describedherein to be conducted. Controller(s) 26 are coupled with the variouspower sources, heating systems, pumps, robotics and gas flowcontrollers, or valves of the reactor, as will be appreciated by theskilled artisan. By way of example, controller 26 can be configured tocontrol gas flow of a silicon precursor, a nitrogen and/or oxygenreactant, optionally a hydrogen reactant, and a fluorine reactant intoat least one of one or more reaction chambers to form one or more of asilicon nitride layer and a silicon oxide layer on a surface of asubstrate.

In some embodiments, a dual chamber reactor (two sections orcompartments for processing substrates disposed close to each other) canbe used, wherein a reactant gas and a noble gas can be supplied througha shared line, whereas a precursor gas is supplied through unsharedlines.

The example embodiments of the disclosure described above do not limitthe scope of the invention, since these embodiments are merely examplesof the embodiments of the invention. Any equivalent embodiments areintended to be within the scope of this invention. Indeed, variousmodifications of the disclosure, in addition to those shown anddescribed herein, such as alternative useful combinations of theelements (e.g., steps) described, may become apparent to those skilledin the art from the description. Such modifications and embodiments arealso intended to fall within the scope of the appended claims.

What is claimed is:
 1. A method of depositing one or more of siliconnitride and silicon oxide onto a surface of a substrate within areaction chamber, the method comprising the steps of: providing afluorine reactant to the reaction chamber for a fluorine reactant pulse;providing a silicon precursor to the reaction chamber for a siliconprecursor pulse; providing one or more of a nitrogen reactant and anoxygen reactant to the reaction chamber for a reactant pulse; andoptionally providing a hydrogen reactant to the reaction chamber for ahydrogen reactant pulse.
 2. The method of claim 1, wherein the siliconprecursor comprises one or more of a silane, a halogensilane, and anorganosilane.
 3. The method of claim 2, wherein the silicon precursorcomprises the halogensilane and the halogensilane comprises one or moreof dichlorosilane, diiodosilane, hexachlorodisilane,octachlorotrisilane, dibromosilane, tribromosilane, trichlorosilane(HSiCl₃), chlorosilane (H₃SiCl), silicon tetrachloride (SiCl₄),bromosilane (H₃SiBr), triiodosilane (HSiI₃), iodosilane (H₃SiI),diiiodosilane (H₂Si2I₄), H₄Si₂I₂, and H₅Si₂I.
 4. The method of claim 2,wherein the silicon precursor comprises the organosilane and theorganosilane comprises one or more of an aminosilane and a heterosilane.5. The method of claim 1, wherein the silicon precursor comprises one ormore of tris(dimethylamino)silane, bis(tert-butylamino)silane,di(sec-butylamino)silane, trisilylamine, neopentasilane,bis(dimethylamino)silane, (dimethylamino)silane(DMAS),bis(diethylamino)silane (BDEAS), bis(ethylmethylamino)silane (BEMAS),tetrakis(dimethylamino)silane (TKDMAS), trimethylsilane (SiH(CH₃)₃),tetramethylsilane (Si(Ch₃)₄), silane, tetra(ethoxy)silane (TEOS,Si(OC₂H₅)₄), tris(tert-butoxy)silanol (TBOS), tris(tert-pentoxy)silanol(TPSOL), and dimethyldichlorosilane (Si(OC₂H₅)₄, Si(CH₃)₂(OCH₃)₂). 6.The method of claim 1, wherein the nitrogen reactant comprises one ormore of nitrogen (N₂), N₂O, and NO and/or the oxygen reactant comprisesO₂.
 7. The method of claim 1, wherein the method comprises providing thehydrogen reactant to the reaction chamber and the hydrogen reactantcomprises one or more of hydrogen (H₂), NH₃, N₂H₄, and N₂H₂.
 8. Themethod of claim 1, wherein the fluorine reactant comprises one or moreof NF₃, CF₄, C₂F₆, SF₆, NH₂F, C₃F₈, and F₂.
 9. The method of claim 1,wherein the step of providing one or more of a nitrogen reactant and anoxygen reactant to the reaction chamber comprises continuously providingone or more of a nitrogen reactant and an oxygen reactant during thesteps of providing a silicon precursor, optionally providing a hydrogenreactant, and providing a fluorine reactant.
 10. The method of claim 1,wherein the step of providing one or more of a nitrogen reactant and anoxygen reactant and the step of providing a hydrogen reactant overlapwithin the reaction chamber.
 11. The method of claim 1, wherein the stepof providing a hydrogen reactant and the step of providing a siliconprecursor overlap within the reaction chamber.
 12. The method of claim1, wherein the step of providing a fluorine reactant precedes the stepof providing a silicon precursor.
 13. The method of claim 1, wherein thestep of providing a hydrogen reactant and the step of providing afluorine reactant do not overlap within the reaction chamber.
 14. Themethod of claim 1, wherein a plasma is applied during the step ofproviding one or more of a nitrogen reactant and an oxygen reactant toform one or more of activated nitrogen species and activated oxygenspecies.
 15. The method of claim 1, wherein a plasma is applied duringthe step of providing a hydrogen reactant to form activated hydrogenspecies.
 16. The method of claim 1, wherein a plasma is applied duringthe step of providing a fluorine reactant to form activated fluorinespecies.
 17. The method of claim 1, wherein a temperature of a susceptorduring the step of providing a fluorine reactant is between about −20°C. and about 1000° C. or about 75° C. and about 600° C.
 18. The methodof claim 16, wherein a power to produce activated fluorine speciesduring the step of providing a fluorine reactant is greater than OW andabout 10000 W or about 50 W and about 3000 W.
 19. The method of claim 1,wherein a duration of the fluorine reactant pulse is between about 0.01seconds to about 600 seconds or about 1 second to about 300 seconds. 20.The method of claim 1, wherein a pressure within the reaction chamberduring the fluorine reactant pulse is between about 0.0001 Pa and about101325 Pa or about 10 Pa and about 13333 Pa.
 21. The method of claim 1,wherein the method comprises filling a gap on a surface of the substratewith the one or more of silicon nitride and silicon oxide.
 22. Themethod of claim 1, wherein the method comprises forming a hard mask withthe one or more of silicon nitride and silicon oxide.
 23. A structureformed using the method of claim
 1. 24. A system comprising: one or morereaction chambers; a silicon precursor source; one or more of an oxygenreactant source and a nitrogen reactant source; optionally a hydrogenreactant source; a fluorine reactant source; a plasma power source; anexhaust source; and a controller, wherein the controller is configuredto control gas flow of a silicon precursor, a nitrogen and/or oxygenreactant, optionally a hydrogen reactant, and a fluorine reactant intoat least one of the one or more reaction chambers to form one or more ofa silicon nitride layer and a silicon oxide layer on a surface of asubstrate.